Dispersions and films comprising conducting polymer for optoelectronic devices

ABSTRACT

A dispersion, and a film and optoelectronic devices formed from the dispersion are provided. The dispersion comprising conducting polymer containing particles having a particle size of less than 450 nm, wherein the conducting polymer comprises substituted or unsubstituted, uncharged or charged polymerized units of thieno[3,4-b]thiophene, and wherein a film drop cast from the dispersion has a conductivity from 10 −1  to 10 −6  S/cm measured using the four point probe method.

BACKGROUND OF THE INVENTION

The invention relates to films, dispersions and optoelectronic devicescomprising conducting polymer.

Optoelectronic devices are devices characterized by the interconversionof light and electricity. Optoelectronic devices either produce light oruse light in their operation. Examples of optoelectronic devices includeelectroluminescent assemblies (e.g. light emitting diodes), laser diodeand photovoltaic assemblies (e.g. photodiodes, photodetector and solarcells).

Electroluminescence is nonthermal conversion of electrical energy intolight. An electroluminescent (“EL”) assembly is characterized by theemission of light and the flow of electric current when an electricpotential (or voltage) is applied. Such assemblies include lightemitting diodes (“LEDs”), which are injection type devices. Organic LEDs(OLEDs) comprise organic semiconductors, such as conjugated lowmolecular weight molecules (small molecules) and high molecular weightpolymers.

Organic semiconductors, especially conjugated polymers, combine theoptical and electrical properties of inorganic semiconductors and themechanical strength, such as flexibility, of plastics. Therefore, OLEDshave many advantages over other competing technologies and can be usedin many different applications. For example, OLEDs can be used ininformation displays and general lighting applications.

A photovoltaic (PV) device absorbs light and generates electricity. Theabsorption of light and separation of charges happen in the activematerials in a PV device. Organic materials such as conjugated polymersand small molecules can be used as the active materials in PV devices.Organic material based PV devices offer a potentially cheaperalternative over the traditional silicon based photovoltaic devices,such as solar cells and photodetectors.

A simple OLED comprises electroluminescent or light emitting organicmaterial(s) sandwiched between two electrodes (J. H. Burroughes et al,Nature 347, 539 (1990)), one of which (frequently anode) is transparentto allow light to be extracted from the device and used for display orlighting. When the device is connected to an external voltage/currentsource, holes are injected from the anode and electrons injected fromthe cathode into the light emitting layer. The holes and electrons thenmigrate towards the opposite electrode under the influence of theapplied electric field. In the recombination zone in the organic layer,holes and electrons encounter each other. A fraction of them recombineand form excitons or excited states. Some of the excitons then decayradiatively to the ground state by spontaneous emission and emit light.To improve the device performance, additional layers that can helpinject/transport holes/electrons into the organic layer can be added.(C. W. Tang et al., Appl. Phys. Lett. 51, 913 (1987); P. K. H. Ho, etal., Nature 404,481(1998)).

The multilayer device configuration offers the advantage of being ableto optimize the properties of the materials used for each layer, andadjust the layer thickness according to the property of the materials.However, the cost associated with manufacturing increases commensuratelywith the number of layers. With device design for manufacturability as aguide, a two-layer design becomes the minimum number of layers thatprovides anode-ion buffering and charge-carrier transportdifferentiation (M. T. Bernius et al., Adv. Mater. 12, 1737 (2000)). Ina double layer device, each layer has multiple functions, e.g. chargeinjection/transport or charge transport/emission.

For hole injection/transport layer applications, a number ofsemiconductive materials have been demonstrated in the prior art.Poly(N-vinylcarbazole) (PVK) has been used as hole transport layer insmall molecule OLEDs (X. Z. Jiang et al., Synth. Met. 87, 175 (1997)).Aromatic amines have been used as hole transporting layer (C. W. Tang etal., Appl. Phys. Lett. 51, 913 (1987)). A series of triarylaminecontaining perfluorocyclobutanes (PFCBs) that are in-situ thermallypolymerized have been reported as hole injection/transport layer inOLEDs. The highest occupied molecular orbital (HOMO) level of the PFCBsranges from −5.1 to −5.3 eV, which matches well with the work functionof indium tin oxide (ITO), a commonly used anode for LEDs. Oncepolymerized, the PFCBs are insoluble in most organic solvent, whichenables the fabrication of multilayer LEDs (X. Z. Jiang et al., Adv.Funct. Mater. 12, 745 (2002)). Using a high glass transition temperature(T_(g)) hole transport polymer with triphenyldiamine as the side chain,an OLED with a luminous efficiency of 20 Im/W and an external quantumefficiency of 4.6% at 14 cd/m² has been achieved. The device quantumefficiency can be increased by tuning the ionization potential of thehole transport moieties (G. E. Jabbour et al. IEEE Journal of QuantumElectronics 36 (1),12 (2000)).

Conducting polymers have also been utilized as hole injection/transportmaterial in OLEDs. Yang et al. disclosed the use of polyaniline (PANI)or a combination of PANI and ITO as the transparent anode of a polymerLED with poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene](MEH-PPV), as the active layer (Y. Yang et al., Appl. Phys. Lett. 64,1245 (1994)). Poly(3,4-ethylenedioxythiophene) (PEDOT) has been used tofacilitate hole injection/transport (U.S. Pat. No. 6,391,481). Higginset al disclosed an emeraldine base PANI protonated with polystyrenesulfonic acid as hole transport layer (R. W. T. Higgins et al., Adv.Funct. Mater. 11 (6), 407 (2001)).

OLEDs represent a promising technology for large, flexible, lightweight,flat-panel displays. However, the OLED devices need further improvementfor practical applications. Similarly, the performance of organicphotovoltaic devices needs further enhancement for practicalapplications.

BRIEF SUMMARY OF THE INVENTION

The current invention is a film comprising conducting polymer appliedfrom a dispersion containing particles having a particle size of lessthan 450 nm, wherein the conducting polymer comprises substituted orunsubstituted, uncharged or charged polymerized units ofthieno[3,4-b]thiophene, and wherein a film has a conductivity betweenfrom 10⁻¹ to 10⁻⁶ S/cm, or from 10⁻² to 10⁻⁶ S/cm, or from 10⁻² to 10⁻⁵S/cm when measured from a drop-cast film of the dispersion using thefour point probe method. The film is particularly useful as a holeinjection layer, a hole transport layer or a combined hole injection andhole transport layer in an optoelectronic device.

The film comprising polymerized units of thieno[3,4-b]thiophene can beapplied from a dispersion that contains particles, even in a swollenstate, having a particle size of less than 450 nm, or less than 200 nm.

The invention provides a dispersion comprising conducting polymercontaining particles having a particle size of less than 450 nm, whereinthe conducting polymer comprises substituted or unsubstituted, unchargedor charged polymerized units of thieno[3,4-b]thiophene, and wherein afilm drop cast from the dispersion has a conductivity from 10⁻¹ to 10⁻⁶S/cm measured using the four point probe method.

When a film comprising polymerized units of thieno[3,4-b]thiophene isused as a hole injection layer, hole transport layer, or holeinjection/transport layer for optoelectronic devices such as lightemitting diodes or photovoltaic devices, the device performance can beimproved. Optoelectronic devices comprising the film are also providedby this invention.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between the reaction time at9° C. to form a dispersion, and the conductivity of the film drop castfrom the dispersion.

FIG. 2 is a schematic showing the layers in one embodiment of an organiclight emitting diode (OLED).

FIG. 3 is a schematic showing the layers of one embodiment of aphotovoltaic (PV) device.

FIG. 4 is a graph of the current versus voltage for the PV device ofExample 15.

FIG. 5 is a graph of the current versus voltage for the PV device ofExample 16.

DETAILED DESCRIPTION OF THE INVENTION

One embodiment of the invention is a film comprising conducting polymerapplied from a dispersion containing particles having a particle size ofless than 450 nm, wherein the conducting polymer comprises substitutedor unsubstituted, uncharged or charged polymerized units ofthieno[3,4-b]thiophene, and wherein the film has a conductivity between10⁻¹ to 10⁻⁶ S/cm. The film is particularly useful as a hole injectionlayer, a hole transport layer or a combined hole injection and holetransport layer. The film is particularly useful in an optoelectronicdevice that is capable of the interconversion of light and electricity.

The term dispersion is used herein to describe a system consisting of adisperse phase in a medium. It can be a dispersion, a solution, acolloid, an emulsion or the like. In this invention, the term dispersionis used herein to describe the material used to form the film comprisingthe conducting polymer. It is understood that the material used to formthe film may be a dispersion, a solution, a colloidal, an emulsion, orthe like.

The term film, used herein, shall possess a broad definitionencompassing any coating or deposit of the films of the presentinvention regardless of thickness, shape or structure. In certainembodiments, the thickness is at least 5 nm. Films can be formed bydepositing a monomolecular layer of the composition. Several layers ofthe same or different compositions are also contemplated herein.

It has been found that the thieno[3,4-b]thiophenes of this inventionpolymerize at high polymerization rates in the presence of polyanions,and form stable compositions preferably in solvent having the desiredproperties for optoelectronic applications. Water, or organic solvents,such as, lower alcohols like methanol, ethanol, butanol or isopropanolas well as mixtures of water with said lower alcohols or with otherwater-miscible organic solvents like acetone are suitable as solventsfor the compositions. The preferred solvents are water, or awater/alcohol mixture. The term aqueous medium will be used herein torefer to the solvent when it includes water or a mixture of water andone or more organic solvents used in the dispersions.

The average particle diameter of the particles of the dispersions isless than 450 nm, preferably less than 200 nm.

Accordingly, the present invention relates to dispersions of polymers inthe presence of polyanions, wherein the polymers comprise structuralunits corresponding to the following formula (I):

where R is hydrogen, substituted or unsubstituted (C₁-C₁₈)-alkyl,preferably (C₁-C₁₀)-alkyl, in particular (C₁-C₆)-alkyl, for example,t-butyl, (C₃-C₇)-cycloalkyl, (C₁-C₁₈)-alkyloxy, preferably(C₁-C₁₀)-alkyloxy, or (C₂-C₁₈)-alkyloxy ester, phenyl and substitutedphenyl, and SF₅.

Suitable conductive polymers which may be used in accordance with thepresent invention include undoped or doped, soluble or insolublethieno[3,4-b]thiophene based polymers comprising units of the formula(I), such as, the polymer shown in formula (II)

where

-   -   n represents an integer from 3 to 100 and    -   R is hydrogen, substituted or unsubstituted (C₁-C₁₈)-alkyl,        preferably (C₁-C₁₀)-alkyl, in particular (C₁-C₆)-alkyl, for        example, t-butyl, (C₃-C₇)-cycloalkyl, (C₁-C₁₈)-alkyloxy,        preferably (C₁-C₁₀)-alkyloxy, or (C₂-C₁₈)-alkyloxy ester, phenyl        and substituted phenyl, and SF₅. When R═H, a crosslinking        structure is possible through the R-linked carbon site. The term        poly(thieno[3,4-b]thiophene) will be used to refer to        homopolymers or copolymers comprising structural units        corresponding to formula (I).

The polyanions are anions of polymeric carboxylic acids, such aspolyacrylic acids, polymethacrylic acids or polymaleic acids, andpolymeric sulfonic acids, such as polystyrene sulfonic acids andpolyvinyl sulfonic acids. These polycarboxylic and polysulfonic acidsmay also be copolymers of vinyl carboxylic and vinyl sulfonic acids withother polymerizable monomers, such as acrylates and styrene.

The molecular weight of the polyacids supplying the polyanions ispreferably in the range form 1,000 to 1,500,000, more preferably in therange from 2,000 to 300,000, most preferably from 20,000 to 260,000. Thepolyanions can also be supplied by alkali salts of the polyacids. Thepolyacids or their alkali salts are commercially available, for examplepolystyrene sulfonic acids and polyacrylic acids, or may be produced byknown methods.

The dispersions comprising conducting polymer in the presence ofpolyanions according to the invention are obtained by oxidativepolymerization of units corresponding to formula (I), with oxidizingagents typically used for the oxidative polymerization of pyrrole and/orwith oxygen or air in the presence of the polyacids, preferably inaqueous medium, at temperatures from 4° C. to 50° C., preferably from 8°C. to 22° C., more preferably from 8° C. to 18° C.

For polymerization, the monomers corresponding to formula (I),polyanion(s) and oxidizing agent(s), and other optional components aredissolved or dispersed in an organic solvent, or preferably, in anaqueous medium and the resulting reaction mixture is stirred at thedesired polymerization temperature. Where air or oxygen is used as theoxidizing agent, air or oxygen is introduced into the reaction mixturecontaining the monomers of formula (I), polyacid and, optionally,catalytic quantities of metal salts or other components during the wholepolymerization period.

The reaction mixture may be mixed before and/or during thepolymerization. Mixing can be accomplished by several means includingmechanical means. Preferred mechanical mixing is high shear mixing.Presently, shear mixing from 5000 rpm to 24,000 rpm is preferred. Thepolymerization can be carried out from 10 minutes to 24 hours,preferably from 20 minutes to 4 hours. The time for polymerization ofthe reaction mixture will vary with the composition of the reactionmixture, the temperature and the rate of mixing. The stability of theobtained dispersions may be improved by the addition of dispersingagents like sodium dodecyl sulphonate during or after polymerization.

Suitable oxidizing agents are any of the oxidizing agents suitable forthe oxidative polymerization of pyrrole which are described, forexample, in J. Am. Soc. 85, 454 (1963). For practical reasons, it ispreferred to use inexpensive and easy-to-handle oxidizing agents, forexample iron(III) salts, such as FeCl₃, Fe(ClO₄)₃, Fe₂(SO₄)₃, and theiron(III) salts of organic acids and inorganic acids containing organicresidues, as well as H₂O₂, K₂Cr₂O₇, alkali or ammonium persulfates,alkali perborates, potassium permanganate and copper salts, such ascopper tetrafluoroborate. In addition, it has been found that air andoxygen, optionally in the presence of catalytic quantities of metalions, such as iron, cobalt, nickel, molybdenum and vanadium ions, mayadvantageously be used as oxidizing agents.

The use of the persulfates and the iron(III) salts of organic acids andinorganic acids containing organic residues has the major applicationaladvantage that they are not corrosive.

Examples of iron(III) salts of inorganic acids containing organicresidues are the iron(III) salts of sulfuric acid semiesters of C₁₋₂₀alkanols, for example, the Fe(III) salt of lauryl sulfate.

Examples of iron(III) salts of organic acids are: the Fe(III) salts ofC₁₋₃₀ alkyl sulfonic acids, such as methane or dodecane sulfonic acid;aliphatic C₁₋₂₀ carboxylic acids, such as 2-ethylhexyl carboxylic acid;aliphatic perfluorocarboxylic acids, such as trifluoroacetic acid andperfluorooctanoic acid; aliphatic dicarboxylic acids, such as oxalicacid and aromatic, optionally C₁₋₂₀-alkyl-substituted sulfonic acids,such as benzenesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

Mixtures of the above-mentioned Fe(III) salts of organic acids may alsobe used.

Theoretically, 2 equivalents of oxidizing agent per mol monomer of theformula (I) are required for the oxidative polymerization. In practice,however, the oxidizing agent is used in certain excess, for example inan excess of 0.1 to 2 equivalents per mol monomer.

In the oxidative polymerization reaction, the polyanion to be used inaccordance with the invention are added in such a quantity that, forevery mol monomer corresponding to formula (I), there are 0.01 to 50 andpreferably 0.1 to 30 mol anion groups of the polyanion.

For the oxidative polymerization, the monomers corresponding to formula(I) and the polyanion(s) are dissolved in such a quantity of solventthat stable poly(thieno[3,4-b]thiophene) dispersions are obtained havingsolid contents of 0.05 to 50% by weight and preferably 0.5 to 5% byweight.

To obtain films having better adhesion to the substrate, polymericbinder soluble or suspendable in water, for example polyvinyl alcohol orpolyvinyl acetate dispersions, may also be added to the dispersion.Ammonia or amines may be added to neutralize the dispersion afterpolymerization. After the polymerization, solvents or cosolvents oradditives, such as, surfactant may also be added to the dispersion.

The polyanion(s) may be added to the reaction mixture prior topolymerization or may be added to the dispersion after polymerization.Dispersions may be obtained with less than 0.5 part by weight of theconducting polymer comprising units of formula (I) based on one part byweight of the polyanion(s).

The dispersions used to form the films of this invention may comprisecopolymers, comprising units of thieno[3,4-b]thiophene, and units ofother monomers The monomers useful for forming copolymers includemonomers known to form conducting polymers through oxidativepolymerization, particularly other thiophene monomers. Examples ofuseful monomers used to form conducting polymers that can be added tothe dispersions are disclosed in U.S. Pat. No. 5,300,575, and U.S. Pat.No. 4,959,430 incorporated herein by reference. Monomers used to formother known conducting polymers can be added to the reaction mixtureused to form the dispersion prior to or during the polymerization. Thetotal amount of monomers including the monomers of formula (I) added tothe reaction mixture may be from 0.01 to 30% by weight based on thetotal weight of the dispersion.

Preferred dispersions of the conducting polymers contain less than 10ppm of metal ions and/or less than 10 ppm of anions of inorganic acids.Particularly preferred are dispersions of the conducting polymers thatcontain less than 1 ppm of metal ions and/or less than 1 ppm of anionsof inorganic acids.

It is also possible to add electrically inert organic polymers and/ororganic low molecular weight crosslinking agent to the dispersionscomprising the conducting polymer to adjust the conductivity, andfilm-forming properties.

As shown by the examples herein, the particle size of the dispersionsand the conductivity of films prepared from the dispersions can beadjusted by the composition and the process of preparation of thedispersions (for example, by adjusting the temperature, shear rate, andreaction times). This is important for optoelectronics, e.g. matrixdisplay, particularly for passive matrix display, because crosstalkbetween neighboring pixels might occur due to low surface resistance ofthe films. In this respect, the conductivity of the film can beoptimized for the desired film thickness to yield a film that has asurface resistance necessary to suppress crosstalk.

The inventors have discovered that there is a relationship between thepolymerization reaction time and the conductivity of films cast from theresulting dispersion for a given reaction temperature of the dispersion.FIG. 1 is a graph showing the relationship between the measured dropcast film conductivity (measured from a drop cast film in an argon glovebox using the four point probe method) and the polymerization reactiontime for a reaction mixture at 9° C. used to form a dispersion and filmin accordance with this invention. At higher polymerization temperaturesshorter reaction times would be required to obtain conductivities from10⁻¹ to 10⁻⁶ S/cm. At polymerization temperatures less than 9° C.,longer reaction times would be required to obtain conductivities from10⁻¹ to 10⁻⁶ S/cm. The oxidative polymerizations ofthieno[3,4-b]thiophene in the presence of polyanions can be carried outover a range of polymerization reaction times and temperatures.Preferred polymerization temperatures are from 7° C., to about roomtemperature (22° C.). More preferred polymerization temperatures arefrom 8° C. to 18° C.

It also has been found that by controlling the polymerizationtemperatures and polymerization reaction times not only the conductivityof the doped conducting polymer can be altered but also thefilterability of the aqueous dispersions produced from the oxidativepolymerization. The aqueous dispersions produced between 8° C. and 18°C. can be filtered through a 450 nm pore size filter and a 200 nm poresize filter. Any reference to a filter size herein means the pore sizeof the filter unless otherwise indicated. Filterability denotes a smallparticle size which is important in producing uniform (smooth) filmsmade by spin casting of the aqueous dispersion of the doped conductingpolymer.

The dispersions of the conducting polymer are preferably filteredthrough a filter having a pore size less than or equal to 450 nm beforethe dispersions are used to form films, e.g. by coating onto substratesor other articles. Preferably, the solutions or dispersions are filteredusing filters with pore size less than or equal to 200 nm before thedispersions are used to form films.

The films of this invention are typically applied to an article. Thefilm application or fabrication methods include but are not limited tospin coating, doctor blade coating, ink jet printing, screen printing,thermal transfer printing, microcontact printing or digital printing.Thickness of the film can range from 2 nm to 1000 nm, preferably from 20nm to 500 nm, or more preferably from 50 nm to 200 nm. After the film isdeposited from the dispersion, the film may be heated at a temperaturefrom 50° C. to 250° C., preferably from 100° C. to 200° C. to remove theresidual solvent, or other volatiles preferably in an inert atmosphere.

The films of this invention are useful as a layer in an optoelectronicdevice. The film can be used to form the hole injection layer, holetransport layer or combined hole injection and hole transport layer(which may be referred to hereinafter as a “hole injection/transportlayer”) in an optoelectronic device. Examples of optoelectronic devicesinclude light emitting diodes and photovoltaic devices.

A multiple-layered LED structure is shown in FIG. 2. (As mentionedbefore, an LED 100 may be formed with a light emitting layer between twoelectrodes, in which the light emitting layer assumes a plurality offunctions.) The LED shown in FIG. 2 has a substrate 101, anode 102, holeinjection layer 103, hole transport layer 104, light emitting layer 105,electron transport layer 106, electron injection layer 107, and cathode108. When making display or lighting devices, at least one of the anode102 and the cathode 108 is transparent. Since the device is sensitive tomoisture/oxygen, the device is normally hermetically encapsulated fordifferent applications. The LED shown in FIG. 2 is one embodiment.Alternative embodiments may consist of fewer or more layers. If thereare fewer individual layers, at least one of the remaining layersassumes a plurality of functions.

Suitable materials for the substrate 101 which may be considered a layerof the device, include glass, metal foil, plastics such as poly(ethyleneterephthalate), poly(ethylene naphthalate), polyester, polysulfone,polyimide, polycarbonate, polyacrylate, polyarylate, and the like. Thesubstrate 101 will be transparent if the light is to be extracted fromthe device through the anode 102 in the embodiment shown in FIG. 2. Inthe case of light being extracted through the cathode 108, a transparentcathode is used and a non-transparent substrate such as metal foil, canbe used as the substrate 101. An encapsulation layer (not shown) istypically provided to seal the LED. If the encapsulation layer coversthe layer from which light is emitted or extracted, it is preferably atransparent layer. Useful materials, such as glass and metal plates forthe encapsulation layer are known in the art.

Suitable anode materials for anode 102 include metal oxides such as tinoxide, ITO, zinc oxide, doped zinc oxide, a semitransparent thin film ofmetals such as Au, Pt, Cu, and Ag, etc., or conductive polymers such aspolyaniline, poly(3,4-ethylenedioxythiophene) (PEDOT), U.S. Pat. No.5,766,515, and U.S. Pat. No. 6,083,635, polythiophene, polypyrrole, andthe like.

The cathode 108 can be a material containing any metal or nonmetalcapable of injecting electrons into the light emitting layer. Thecathode normally has a lower work function than the anode material.Suitable materials for the cathode 108 are low work function metals suchas aluminum, indium, calcium, barium, magnesium, silver, lithium, or thelike, alloy such as Mg:Ag, and a combination of salts and metals, suchas, LiF/Al, NaCl/Al, or LiF/Ca/Al, or the like. Semitransparentcathodes, such as, very thin layers of the above mentioned metals incombination with ITO, can be used to fabricate OLEDs that emit lightthrough the cathode. The cathode layer is usually applied by a physicalvapor deposition process such as thermal deposition, plasma deposition,e-beam deposition, or sputtering.

The light-emitting layer 105 may contain any organic electroluminescentmaterial. Suitable materials for the light emitting layer includepolymeric materials such as those described in U.S. Pat. No. 5,247,190(to Friend et al.), U.S. Pat. No. 5,408,109 (to Heeger et al.), U.S.Pat. No. 5,962,631 (to Woo et al.), which are incorporated herein byreference, poly(phenylene vinylene)s, such as, poly(2-methoxy,5-(2′-ethyl-hexyloxy)-p-phenylene-vinylene) (MEH-PPV) and Covion's SuperYellow, polyfluorenes, such as, poly(9,9-dialkyl fluorene),poly(9,9-dialkyl fluorene)-co-2,1,3-benzothiadiazole,poly(9,9-diakylfluorene)-co-2,1,3-benzothiadiazole-co-thiophene,poly(para-phenylene), spiropolyfluorenes, and the like; small molecules,such as, 8-hydroxyquinoline aluminium (Alq₃), laser dyes, europiumcomplex, and dendrimers, (J. M. Lupton et al., Adv. Mater. 13(4), 258(2001)) and those described in, for example, U.S. Pat. No. 4,356,429 toTang et al., incorporated herein by reference. Phosphorescent compounds,e. g., platinum octaethyl porphyrin (PtOEP),bis(2-(2′-benzothienyl)pyridinato-N,C^(3′))acetylacetonate) Iridium(III), and tris(2-(4-tolyl)phenylpyridine) Iridium (III), which canutilize triplet excitons, and hence yield higher efficiency, can also beused for the light emitting layer 105. A blend or mixture of two or moresmall molecule or polymer light emitting materials can also be used. Thesmall molecules can also be doped into or blended with polymers.

The light-emitting materials may be dispersed in a matrix of othermaterial(s). The light-emitting layer generally has a thickness of 40 to400 nm.

The light emitting layer can be applied (onto the hole transport layer,hole injection layer or hole injection/transport layer) from solutionsby any casting method, such as, spin-coating, ink-jet printing, screenprinting, or digital printing. The light emitting layer can also beapplied by a thermal transfer process. In the case of small molecules,the layer can be applied by thermal evaporation, or low pressure organicvapor phase deposition.

The film of this invention can be used as either the hole injectionlayer (HIL) 103 or hole transport layer (HTL) 104 or can be used toreplace the HIL 103 and HTL 104 as shown in FIG. 2 with a single holeinjection/transport layer (not shown). The film of this invention whenused as a hole injection/transport layer in one embodiment forms a clearinterface between the anode layer 102 and the light emitting layer 105.In the preferred embodiments described herein, the film of thisinvention is used as both the HIL and HTL in the LED; however, the filmcould be used in an LED as the HIL with a separate and/or different HTLtherein, or the film could be used in an LED as the HTL with a separateand/or different HIL therein. In alternative embodiments, an electronblocking layer can be inserted between the light emitting layer and theHIL or HTL (either or both of which may comprise films of thisinvention) to prevent electrons from reaching one or both of thoselayers.

Since the film of this invention may have a more favorable work functioncompared with commonly used anode material ITO, the film may improve theinjection of holes within the LED devices. The film of this inventionmay also have a higher conductivity compared with the light emittingpolymer layer; therefore, it may also function as a hole transportlayer. Furthermore, the film of this invention may act as a bufferlayer, because the electric field in the film may be lower than in thelight emitting layer, which will slow down the diffusion of ions such asIn³⁺.

A photovoltaic (PV) device is a device that absorbs light and generateselectricity. FIG. 3 shows the structure of one embodiment of a PVdevice, comprising substrate 201, anode 202, hole transporting layer203, semiconductive hole transporting layer 204, semiconductive electrontransporting layer 205, and cathode 206. Alternative embodiments of PVdevices may have fewer or more layers than are shown in FIG. 3. In thecase of a bulk heterojunction PV device, layers 204 and 205 can besubstituted with a layer of interpenetrating network of thesemiconductive hole transporting and electron transporting materials toincrease the interfacial area where charge separation takes place.

For a PV, the substrate 201, the anode 202, and the cathode 206, can bethe same materials as those described for the substrate 101, the anode102, and the cathode 108 for the LED above, respectively. The holetransport layer 203 can comprise the film of this invention.

The semiconductive hole transporting layer 204 may be made of smallmolecules or polymers having hole transporting properties, such asMEH-PPV (G. Yu et al., J. of Electronic Materials 23, 925(1994)),phthalocyanine, and aryl amines.

The semiconductive electron transporting layer 205 may be made of smallmolecules or polymers having electron transporting properties, such asCN-PPV (J. J. M. Halls et al. Nature 376, 498, 1995), N,N′-bis(2,5-di-tert-butylphenyl-3,4,9,10-perylenedicarboximide, andperylene-3,4,9,10-tetracarboxylic-4,4,9,10-dianhydride (PTCDA). Thecombination of semiconductive hole transporting material and electrontransporting material should be selected based on their HOMO and LUMOenergy level alignment, such that charge separation from excitonsgenerated in one or both of the materials will be factilitated at theinterface of the two materials.

The light emitting diode or photovoltaic devices of the invention can beproduced by the methods disclosed in the prior art, known to a person ofskill in the art or as described in the examples below.

EXAMPLES Example 1 Poly(thieno[3.4-b]thiophene):poly(styrene sulfonicacid) (PTT) Dispersion Prepared at Room Temperature, Film, and OLED(Comparative Example)

0.051 g (0.364 mmol) of thieno[3,4-b]thiophene and 0.424 g of 70,000 Mw(weight average molecular weight) poly(styrenesulfonic acid) solution,30 wt % in water, was added to a 10 mL two neck flask. 9.79 g ofde-ionized water was added before stirring with a teflon stir bar atapproximately 200 rpm. Polymerization was caused by 0.160 g of ferricsulfate hydrate added to the reaction flask while maintaining stirring.The reaction was carried out for 24 hours at 22° C. before the mixturewas purified by passing sequentially through 5 g of Amberlite IR-120 and5 g IRA-900 ion exchange resins, resulting in a deep green-blue aqueousPTT dispersion. The dispersion is hereafter referred to as Dispersion 1.Dispersion 1 was not filterable with a 450 nm filter. A thin film wasprepared by drop cast 0.5 mL of Dispersion 1 onto 1″×1″ glass substrate.The film was dried in air and annealed at 160° C. for 30 minutes undernitrogen protection. The conductivity of the film was 1.60×10⁻³ S/cm,measured by four point probe method in an argon filled glove box.

A light emitting polymer solution of MEH-PPV, (ADS130RE from AmericanDye Source, Inc.) in toluene was prepared by dissolving 25.6 mg ofMEH-PPV in 4.25 g of toluene and then filtered with a 1000 nm PVDF(Polyvinylidene fluoride) filter. The solution is hereafter referred toas Solution A. An ITO coated glass substrate (2.5×2.5×0.7 cm, surfaceresistance ˜12 Ω/square) was cleaned by ultrasonication sequentially indetergent, de-ionized water, methanol, isopropanol, and acetone; eachfor 5 to 10 minutes. The ITO substrate was allowed to dry betweendifferent cleaning solvents. Then the ITO substrate was treated withoxygen plasma in an SPI Prep II plasma etcher for about 10 minutes.After that, the ITO substrate was spin coated with Dispersion 1 at 800rpm for 2 minutes followed by 2000 rpm for 20 seconds on a Laurell ModelWS-400-N6PP spinner to form the HIL. Since Dispersion 1 was notfilterable, it was used without filtration. The thickness of the PTTlayer was about 30 nm. The PTT coated ITO substrate was then annealed at180° C. for 15 minutes under nitrogen protection. Then a layer of about70-nm-thick MEH-PPV was spin coated onto the HIL from Solution A at aspin rate of 1500 rpm. The sample was then transferred into the chamberof a vacuum evaporator, which was located inside an argon atmosphereglove box. A layer of 20 nm thick Ca was vacuum deposited at below1×10⁻⁷ Torr through a mask at a rate of 1.5˜2.0 Å/s, and another layerof 100 nm thick Ag was vacuum deposited on top of Ca as a protectinglayer. The active area of the device was about 6.2 mm². The LED devicewas then moved out of the glove box for testing in air at roomtemperature. Thicknesses were measured on a KLA Tencor P-15 Profiler.Current-voltage characteristics were measured on a Keithley 2400SourceMeter. Electroluminescence (EL) spectrum of the device wasmeasured using an Oriel InstaSpec IV CCD camera. The power of ELemission was measured using a Newport 2835-C multi-function opticalmeter in conjunction with a calibrated Si photodiode. Brightness wascalculated using the EL forward output power and the EL spectrum of thedevice, assuming Lambertian distribution of the EL emission. The deviceshowed very high leakage current and poor performance. The devicereached 1 cd/m² at 4 V, with a maximum external quantum efficiency ofonly 0.16%. At a current density of 100 mA/cm², the device showed abrightness of only 150 cd/m². At a current density of 1000 mA/cm², thebrightness was only 2000 cd/m².

Example 2 PTT Dispersion Prepared at Room Temperature With High ShearMixing, Film, and OLED

Using a 350 mL jacketed Florence flask, 3.5 g of 244,000 Mwpoly(styrenesulfonic acid) was dissolved in situ in approximately 30 mlof distilled water. 0.98 g (6.99 mmol) of thieno[3,4-b]thiophene wasadded to the flask followed by sufficient distilled water to make up a350 gram reaction mass. Stirring was accomplished using an IKA TurraxT-25 rotor stator at 11,000 rpm. Polymerization was caused by 3.37 g offerric sulfate hydrate added to the reaction flask while maintainingstirring. Reaction was carried out for 2 hours at 27° C. Temperature wasmaintained using a thermostated recirculating fluid through the jacketedportion of the reaction flask. The reaction mixture was purified bypassing sequentially through 17.5 g of Amberlite IR-120 and 17.5 gIRA-900 ion exchange resins, resulting in a deep green-blue aqueous PTTdispersion. The dispersion is hereafter referred to as Dispersion2.Dispersion 2 was filterable with a 450 nm filter. A thin film ofDispersion 2 was prepared and the conductivity of the film measured thesame way as in Example 1. The conductivity was 8.94×10⁻³ S/cm.

An OLED device was fabricated and tested in the same way as Example 1except that Dispersion 2 was used to spin coat the HIL. Dispersion 2 wasfiltered with a 450 nm PVDF filter before spin coating. The thickness ofthe PTT layer was about 30 nm. The device reached 1 cd/m² at 2.6 V, witha maximum external quantum efficiency of 0.55%. At a current density of100 mA/cm², the device showed a brightness of 850 cd/m². At a currentdensity of 1000 mA/cm², the brightness was 7,900 cd/m². The deviceshowed relatively high leakage current.

Example 3 PTT Dispersion Prepared at Room Temperature With High ShearMixing, Film and OLED

0.51 g (3.64 mmol) of thieno[3,4-b]thiophene and 4.33 g of 70,000 Mwpoly(styrenesulfonic acid) solution, 30 wt % in water, was added to a100 mL jacketed two neck flask. Sufficient distilled water to make up a100 gram reaction mass was added before stirring with an IKA Turrax T8rotor stator at 12,000 rpm. Polymerization was caused by 1.72 g offerric sulfate hydrate added to the reaction flask while maintainingstirring. Reaction was carried out for 1 hour at 22° C. Temperature wasmaintained using a thermostated recirculating fluid through the jacketedportion of the reaction flask. The reaction mixture was purified bypassing sequentially through 15 g of Amberlite IR-120 and 15 g IRA-900ion exchange resins. The resultant dispersion is hereafter referred toas Dispersion 3.Dispersion 3 was filterable with a 450 nm filter. A thinfilm of Dispersion 3 was prepared and the conductivity of the filmmeasured the same way as in Example 1.The conductivity was 1.82×10⁻²S/cm.

An OLED device was fabricated and tested in the same way as Example 1except that Dispersion 3 was used to spin coat the HIL. Dispersion 3 wasfiltered with a 450 nm PVDF filter before spin coating. The thickness ofthe PTT layer was about 30 nm. The device reached 1 cd/m² at 2.5 V, witha maximum external quantum efficiency of 0.55%. At a current density of100 mA/cm², the device showed a brightness of 1,000 cd/m². At a currentdensity of 1000 mA/cm², the brightness was 8,700 cd/m². The device alsoshowed relatively high leakage current.

Example 4 PTT Dispersion Prepared at 4° C. With High Shear Mixing, Filmand OLED

1.73 g (12.34 mmol) of thieno[3,4-b]thiophene and 15.1 g of 70,000 Mwpoly(styrenesulfonic acid) solution, 30 wt % in water, was added to a350 mL jacketed Florence flask. Sufficient distilled water to make up a350 gram reaction mass was added before stirring with an IKA Turrax T25rotor stator at 11,000 rpm. Polymerization was caused by 6.02 g offerric sulfate hydrate added to the reaction flask while maintainingstirring. Reaction was carried out for 1 hour at 4° C. Temperature wasmaintained using a thermostated recirculating fluid through the jacketedportion of the reaction flask. The reaction mixture was purified bypassing sequentially through 50 g of Amberlite IR-120 and 50 g IRA-900ion exchange resins. The resultant dispersion is hereafter referred toas Dispersion 4.Dispersion 4 was filterable with a 200 nm filter. A thinfilm of Dispersion 4 was prepared and the conductivity of the filmmeasured the same way as in Example 1. The conductivity was 1.64×10⁻⁶S/cm.

An OLED device was fabricated and tested in the same way as Example 1except that Dispersion 4 was used to spin coat the HIL. Dispersion 4 wasfiltered with a 450 nm PVDF filter before spin coating. The thickness ofthe PTT layer was about 20 nm. The device reached 1 cd/m² at 2.5 V, witha maximum external quantum efficiency of 0.58%. At a current density of100 mA/cm², the device showed a brightness of 830 cd/m². Due to the lowconductivity of the PTT, the brightness of the device was limited. Themaximum brightness of the device was 1,700 cvd/m² at a current densityof 260 mA/cm² and 11 V.

Example 5 PTT Dispersion Prepared at 9° C. With High Shear Mixing, Filmand OLED

A dispersion was prepared using the same procedure as in Example 4,except that the reaction was carried out for 2.5 hours at 9° C. Thedispersion is hereafter referred to as Dispersion 5. Dispersion 5 wasfilterable with a 200 nm filter. A thin film was prepared usingDispersion 5 and the conductivity of the film measured the same way asin Example 1. The conductivity was 2.16×10⁻³ S/cm.

An OLED device was fabricated and tested in the same way as Example 1except that Dispersion 5 was used to spin coat the HIL. Dispersion 5 wasfiltered with a 450 nm PVDF filter before spin coating. The thickness ofthe PTT layer was about 30 nm. The device reached 1 cd/m² at 2.5 V, witha maximum external quantum efficiency of 0.77%. At a current density of100 mA/cm², the device showed a brightness of 1,300 cd/m². At a currentdensity of 1000 mA/cm², the brightness was 9,280 cd/m².

Example 6 PTT Dispersion Prepared at 9° C. With High Shear Mixing, Filmand OLED

A dispersion was prepared using the same procedure as in Example 4,except that the reaction was carried out for 2.75 hours at 9° C. Thedispersion is hereafter referred to as Dispersion 6.Dispersion 6 wasfilterable with a 200 nm filter. A thin film of Dispersion 6 wasprepared and the conductivity of the film measured the same way as inExample 1. The conductivity was 9.27×10⁻⁴ S/cm.

An OLED device was fabricated and tested in the same way as Example 1except that Dispersion 6 was used to spin coat the HIL. Dispersion 6 wasfiltered with a 0.45 PVDF filter before spin coating. The thickness ofthe PTT layer was about 30 nm. The device reached 1 cd/m² at 2.3 V, witha maximum external quantum efficiency of 0.73%. At a current density of100 mA/cm², the device showed a brightness of 1,440 cd/m². At a currentdensity of 1000 mA/cm², the device showed a brightness of 11,550 cd/m².

Example 7 PTT Dispersion Prepared at 9° C. With High Shear Mixing, Filmand OLED

A dispersion was prepared using the same procedure as in Example 4,except that 0.875 g (6.24 mmol) of thieno[3,4-b]thiophene was used andthe reaction was carried out for 2.75 hours at 9° C. The dispersion ishereafter referred to as Dispersion 7. Dispersion 7 was filterable witha 200 nm filter. A thin film of Dispersion 7 was prepared and theconductivity of the film measured the same way as in Example 1. Theconductivity was 3.24×10⁻³ S/cm.

An OLED device was fabricated and tested in the same way as Example 1except that Dispersion 7 was used to spin coat the HIL. Dispersion 7 wasfiltered with a 450 nm PVDF filter before spin coating. The devicereached 1 cd/m² at 2.2 V, with a maximum external quantum efficiency of0.76%. At a current density of 100 mA/cm², the device showed abrightness of 1,360 cd/m². At a current density of 1000 mA/cm², thebrightness was 10,400 cd/m².

Example 8 PTT Dispersion Prepared at 9° C. With High Shear Mixing, Filmand OLED

A dispersion was prepared following the same procedures as in Example 4,except that 3.5 g (24.96 mmol) of thieno[3,4-b]thiophene and 30.2 g of70,000 Mw poly(styrenesulfonic acid) solution were used, 12.0 g offerric sulfate hydrate was added, the reaction was carried out for 2.5hour at 9 C., and the purification used 100 g of Amberlite IR-120 and100 g of IRA-900 ion exchange resins. The dispersion is hereafterreferred to as Dispersion 8. A thin film of Dispersion 8 was preparedand the conductivity of the film measured the same way as in Example 1.The conductivity was 2.32×10⁻⁴ S/cm.

An LED device was fabricated and tested in the same way as in Example 1except that Dispersion 8 was used to spin coat the HIL. Dispersion 8 wasfiltered with a 450 nm PVDF filter before spin coating. The thickness ofthe PTT layer was about 30 nm. The device reached 1 cd/m² at 2.1 V, witha maximum external quantum efficiency of 0.69%. At a current density of100 mA/cm², the device showed a brightness of 1,330 cd/m². At a currentdensity of 1000 mA/cm², the brightness was 9,070 cd/m².

Example 9 PTT Dispersion Prepared at 9° C. With High Shear, Film andOLED (Comparative Example)

A dispersion was prepared following the same procedures as in example 4,except that 0.46 g (3.28 mmol) of thieno[3,4-b]thiophene and 30.5 g of70,000 Mw poly(styrenesulfonic acid) solution were used, 1.7 g of ferricsulfate hydrate was added, the reaction was carried for 3.5 hours at 9°C., and the purification used 15 g of Amberlite IR-120 and 15 g IRA-900ion exchange resins. The dispersion is hereafter referred to asDispersion 9. Dispersion 9 was filterable with a 200 nm filter. A thinfilm of Dispersion 9 was prepared and the conductivity of the filmmeasured the same way as in Example 1. The conductivity was 5.85×10⁻⁷S/cm.

An OLED device was fabricated and tested the same way as in Example 1except that Dispersion 9 was used to spin coat the HIL. Dispersion 9 wasfiltered with a 450 nm PVDF filter before spin coating. The thickness ofthe PTT layer was about 30 nm. The device showed very poor performance.Only very low current could be passed through the device. The devicereached 1 cd/m² at 3.4 V, with a maximum external quantum efficiency of0.59%. Due to the low conductivity of the PTT film, the emission of thedevice was very weak. The maximum brightness was 150 cd/m² at a currentdensity of 51.5 mA/cm² and 11.9 V.

Example 10 PTT Dispersion Prepared at 15° C. With High Shear Mixing,Film and OLED

A dispersion was prepared following the same procedures as in Example 3,except that the reaction was carried for 1 hour at 15° C. The dispersionis hereafter referred to as Dispersion 10. Dispersion 10 was filterablewith a 200 nm PVDF filter. A thin film of Dispersion 10 was prepared andthe conductivity of the film measured the same way as in Example 1. Theconductivity was 8.10×10⁻⁴ S/cm.

A light emitting polymer solution of MEH-PPV ADS130RE from American DyeSource, Inc.) in toluene was prepared by dissolving 22.5 mg of MEH-PPVin 3.15 g of toluene on a hot plate at 60° C. for 2 hr, and thenfiltered with a 1000 nm filter. The solution is hereafter referred to asSolution B.

An OLED device was fabricated and tested the same way as in Example 1except that Dispersion 10 was used to spin coat the HIL and Solution Bwas used to spin coat (at a spin rate of 2000 rpm) the 70-nm-thickMEH-PPV. Dispersion 10 was filtered with a 450 nm PVDF filter beforespin coating. The thickness of the PTT layer was about 30 nm. The devicereached 1 cd/m² at 2.2 V, with a maximum external quantum efficiency of1.35%. At a current density of 100 mA/cm², the device showed abrightness of 1,780 cd/m². At a current density of 1000 mA/cm², thebrightness was 17,600 cd/m².

Example 11 PTT Dispersion Prepared at 15° C. With High Shear Mixing,Film and OLED

A dispersion was prepared following the same procedures as in Example 3,except that the reaction was carried for 20 minutes at 15° C. Thedispersion is hereafter referred to as Dispersion 11. Dispersion 11 wasfilterable with a 200 nm filter. A thin film of Dispersion 11 wasprepared and the conductivity of the film measured the same way as inExample 1. The conductivity was 1.73×10⁻⁶ S/cm.

An OLED device was fabricated and tested the same way as in Example 10except that Dispersion 11 was used to spin coat the HIL. Dispersion 11was filtered with a 450 nm PVDF filter before spin coating. Thethickness of the PTT layer was about 30 nm. The device reached 1 cd/m²at 2.4 V, with a maximum external quantum efficiency of 1.15%. At acurrent density of 100 mA/cm², the device showed a brightness of 1,590cd/m². The maximum brightness was 5,160 cd/m² at a current density of520 mA/cm² and 9.5 V.

Example 12 Film and OLED of PEDOT (Comparative Example)

A thin film of PEDOT was prepared using an electronic grade Baytron P Al4083 PEDOT dipersion (from Bayer Corp.), and the conductivity of thefilm measured the same way as in Example 1. The conductivity was1.83×10⁻³ S/cm.

An OLED device was fabricated and tested the same way as in Example 1except that Baytron P Al 4083 PEDOT dispersion was used to spin coat theHIL at a spin rate of 2500 rpm. The PEDOT dispersion was filtered with a450 nm PVDF filter before spin coating. The thickness of the PEDOT layerwas about 40 nm. The device reached 1 cd/m² at 2.1 V, with a maximumexternal quantum efficiency of 0.63%. At a current density of 100mA/cm², the device showed a brightness of 1,260 cd/m². At a currentdensity of 1000 mA/cm², the device showed a brightness of 10,400 cd/m².

Example 13 Film and OLED of PEDOT (Comparative Example)

A thin film of PEDOT was prepared from electronic grade Baytron P CH8000PEDOT dispersion (from Bayer Corp.), and the conductivity of the filmmeasured the same way as in Example 1. The conductivity was 2.79×10⁻⁵S/cm.

An OLED device was fabricated and tested the same way as in Example 1except that electronic grade Baytron P CH8000 PEDOT dispersion was usedto spin coat the HIL at a spin rate of 4000 rpm. The PEDOT dispersionwas filtered with a 450 nm PVDF filter before spin coating. Thethickness of the PEDOT layer was about 45 nm. The device reached 1 cd/m²at 2.2 V, with a maximum external quantum efficiency of 0.64%. At acurrent density of 100 mA/cm², the device showed a brightness of 1,040cd/m². The maximum brightness was 3,050 cd/m² at a current density of460 mA/cm² and 8.3 V.

Example 14 Triplet Emitter and PTT Based OLED

A solution was prepared by dissolving 63.0 mg poly(N-vinylcarbazole)(from Aldrich), 27.0 mg2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (from Aldrich),and 4.8 mg of triplet emitter tris(2-(4-tolyl)phenylpyridine) iridium(III) (from American Dye Source, Inc.) in 4.0 g chlorobenzene. Thesolution was filtered with a 200 nm filter and hereafter referred to asSolution C.

An OLED device was fabricated and tested the same way as in Example 1,except that the HIL was fabricated by spin coating Dispersion 2 (afterbeing filtered with a 450 nm PVDF hydrophilic filter) at 1500 rpm for 1minute and then annealed at 200° C. for 5 minutes under nitrogenprotection, and the light emitting layer (135 nm thick) was spin coatedfrom Solution C at a spin rate of 1000 rpm. The device turn-on voltagewas 13.0 V, with a maximum efficiency of 4.5%, and a maximum brightnessof 28,400 cd/m².

Discussion of LED Examples

Table 1 summarizes the conductivity, filterability and deviceperformance of Examples 1 to 13. Examples 1, 9, 12 and 13 areComparative Examples. In the table, V_(on) is the voltage at which thedevice reaches a brightness of 1 cd/m². A lower V_(on) is desirablebecause it implies a lower operation voltage and, consequently, a higherpower efficiency. The external quantum efficiency (EQE) is the number ofphotons emitted per electron injected. The maximum EQE's of the devicesare listed. High efficiency is

TABLE 1 Summary of conductivities and performance ofITO/HIL/MEH-PPV/Ca/Ag devices. Example HIL Filterability σ (S/cm)^(b))V_(on) (V)^(c)) EQE_(max) ^(d)) B₁₀₀ (cd/m²)^(e)) B₁₀₀₀ (cd/m²)^(f)) R₅^(g)) Example 1 PTT N/F^(a)) 1.60E−3 4.0 0.16% 150 2000 1.4 Example 2PTT 0.45 μm 8.94E−3 2.6 0.55% 850 7,900 75 Example 3 PTT 0.45 μm 1.82E−22.5 0.55% 1,000 8,700 156 Example 9 PTT  0.2 μm 5.85E−7 3.4 0.59%N/A^(h)) N/A^(h)) 22 Example 4 PTT  0.2 μm 1.64E−6 2.5 0.58% 830N/A^(h)) 740 Example 11 PTT  0.2 μm 1.73E−6 2.4 1.15% 1590 N/A^(h)) 1750Example 5 PTT  0.2 μm 2.16E−3 2.5 0.77% 1,300 8,200 635 Example 6 PTT 0.2 μm 9.27E−4 2.3 0.73% 1,440 11,550 1840 Example 7 PTT  0.2 μm3.24E−3 2.2 0.76% 1,360 10,400 380 Example 8 PTT  0.2 μm 2.32E−4 2.10.69% 1,330 9,070 7130 Example 10 PTT  0.2 μm 8.10E−4 2.2 1.35% 178017,600 6800 Example 12 PEDOT 0.45 μm 1.83E−3 2.1 0.63% 1,260 10,400 2650Example 13 PEDOT 0.45 μm 2.79E−5 2.2 0.64% 1,040 N/A^(h)) 2310 ^(a))Notfilterable with 0.45 μm filter; ^(b))Conductivity; ^(c))Voltage at whichthe device reach brightness of 1 cd/m²; ^(d))Maximum external quantumefficiency; ^(e))Brightness at current density of 100 mA/cm²;^(f))Brightness at current density of 1000 mA/cm²; ^(g))Rectificationratio at ±5 V; ^(h))The device could not support the specified currentdensity.desirable. The brightnesses of the devices at current densities of 100and 1000 mA/cm² are also listed, a larger number implies a brighter andmore efficient device. The rectification ratios R₅ at ±5 V are alsolisted. R₅ is the ratio of the device current at +5 V to the devicecurrent at −5 V. Because a device with lower leakage current is ideal, alarge value of R₅ is desirable.

In Example 1 (Comparative Example), the dispersion was not filterablewith a 450 nm filter, and the LED showed high operation voltage (4.0 V),low efficiency (0.16%), very high leakage current, and almost norectification up to 5 V (R₅=1.4). The dispersions of this invention arefilterable by a 450 nm filter. However, if the conductivity is too low(<1×10⁻⁶ S/cm), the device performance is also poor, with higheroperation voltage and lower maximum brightness because the device cannotsupport high current density due to the low conductivity of the PTTlayer. It was also surprisingly found that several of the PTT baseddevices (Examples 5, 6, 7, 8, 10, and 11) achieved better performancethan PEDOT based devices (Examples 12 and 13).

Additionally, Example 14 is a dispersion, film and LED of this inventionthat was made using phosphorescent emitter, small moleculetris(2-(4-tolyl)phenylpyridine) iridium (III). Phosphorescent emitterbased devices can utilize the triplet excitons, therefore, the devicehas a higher efficiency (4.5%). This example demonstrates that the PTTfilm can be used for phosphorescent emitter based OLEDs.

Example 15 Photovoltaic Device Using PTT as the Hole Transporting Layer(HTL)

A solution was prepared by dissolving 8.2 mg of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (CAS#65181-78-4, from Aldrich),7.6 mg of N,N′-bis(2,5-di-tert-butylphenyl-3,4,9,10-perylenedicarboximide (CAS#83054-80-2, from Aldrich), 7.2 mg PAE-2 (a poly(arylene ether) (U.S.Pat. No. 5,658,994) and 7.2 mg of Ardel D100 polyarylate (PAL) in 1.53 gof chlorobenzene and filtered with a 0.2 μm filter. The solution isreferred to as Solution D. An ITO substrate was cleaned and treated withoxygen plasma as in Example 1. The ITO substrate was spin coated withDispersion 2 at a spin rate of 1000 rpm and then annealed at about 160°C. for 15 minutes under nitrogen protection. Then Solution D was appliedonto the PTT layer at a spin rate of 1000 rpm. Finally, the sample wasmasked, and a layer of 150-nm-thick Al was deposited via thermal vacuumevaporation at a pressure of 1.1×10⁻⁷ Torr. The active area of thedevice was about 7 mm². The finished device was connected to a Keithley2400 SourceMeter (ITO side to the positive electrode and Al to thenegative electrode), and the current-voltage curves of the device in thedark and under the illumination of a 150 W Xenon lamp were measured. Anopen circuit voltage of 0.6 V and a short circuit current of 15.8 μAwere obtained. The current-voltage characteristics are shown in FIG. 4.

Example 16 Photovoltaic Device Using PTT as the HTL

A solution was prepared by dissolving 6.4 mg of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine, 6.9 mg of N,N′-bis(2,5-di-tert-butylphenyl)-3,4,9,10-perylenedicarboximide, 3.8 mgMEH-PPV, and 3.2 mg of Ardel D100 polyarylate in 1.56 g of chlorobenzeneand filtered with a 0.2 μm filter. The solution is referred to asSolution E. An ITO substrate was cleaned and treated with oxygen plasmaas in Example 1. The ITO substrate was spin coated with Dispersion 2 ata spin rate of 1000 rpm and then annealed at about 160° C. for 15minutes under nitrogen protection. Then Solution E was applied onto thePTT layer at a spin rate of 1000 rpm. Finally, a layer of 150-nm-thickAl was deposited and the device tested the same way as in Example 15. Anopen circuit voltage of 0.4 V and a short circuit current of 11.0 μAwere obtained. The current-voltage characteristics are shown in FIG. 5.A control device without PTT layer was fabricated side by side forcomparison. Under the same illumination condition, the control devicehad an open circuit voltage of less than 0.1 V.

The detailed description and specific examples, while indicatingpreferred embodiments of the invention, are given by way of illustrationonly, since various changes and modifications within the spirit andscope of the invention will become apparent to those skilled in the artfrom this detailed description. All the references and patents citedherein are incorporated in their entirities by reference.

1. An optoeletronic device comprising a substrate, an anode, a cathode and a first film located between the anode and cathode that comprises substituted or unsubstituted, uncharged or charged polymerized units of thieno[3,4-b]thiophene, and wherein the first film has a conductivity from about 10⁻² to 10⁻⁶ S/cm and wherein the device has a rectification ratio of greater than about 75; and a second polymeric film comprising a light emitting polymer that comprises at least one member selected from the group consisting of poly(phenylene vinylene)s and polyfluorenes.
 2. The optoelectronic device of claim 1 wherein the first film comprises particles having a Darticle size of less than about 200 nm.
 3. The optoelectronic device of claim 1 wherein the first film has a conductivity of from about 10⁻² to 10⁻⁵ S/cm.
 4. The optoelectronic device of claim 1 wherein the thieno[3,4-b]thiophene comprises substituted or unsubstituted, uncharged or charged polymerized units of

where R is hydrogen, substituted or unsubstituted (C₁-C₁₈)-alkyl, preferably (C₁-C₁₀)-alkyl, in particular (C₁-C₆)-alkyl, for example, t-butyl, (C₃-C₇)-cycloalkyl, (C₁-C₁₈)-alkyloxy, preferably (C₁-C₁₀)-alkyloxy, or (C₂-C₁₈)-alkyloxy ester, phenyl and substituted phenyl, SF₅.
 5. The optoelectronic device of claim 1 wherein the first film is obtained from a dispersion comprising water, at least one member selected from the group consisting of polymeric sulfonic acids and polystyrene sulfonic acids, and at least one conducting polymer.
 6. The optoelectronic device of claim 5 wherein said member comprises polymeric sulfonic acids.
 7. The optoelectronic device of claim 5 wherein said member comprises polystyrene sulfonic acids.
 8. The optoelectronic device of claim 1 wherein said device comprises a member selected from the group consisting of a light emitting diode, a photovoltaic device, and a laser diode.
 9. The optoelectronic device of claim 1 wherein said first film comprises a hole injection layer.
 10. The optoelectronic device of claim 1 wherein said first film comprises a hole transport layer.
 11. The optoelectronic device of claim 1 wherein said first film comprises a hole injection and hole transport layer.
 12. The optoelectronic device of claim 1 wherein the second film comprises a poly(phenylene vinylene) and said poly(phenylene vinylene) comprises poly(2-methoxy, 5-(2′-ethyl-hexyloxy)-p-phenylene-vinylene).
 13. The optoelectronic device of claim 1 wherein said device comprises a light emitting diode and has a brightness at a current density of 100 mA/cm2 of greater than about 830 cd/m2.
 14. The optoelectronic device of claim 1 wherein the device comprises a photovoltaic device and, said first film comprises a hole transport layer.
 15. An optoeletronic device comprising a substrate, an anode, a cathode, and a first film located between the anode and cathode that comprises substituted or unsubstituted, uncharged or charged polymerized units of thieno[3,4-b]thiophene, and wherein the first film has a conductivity from about 10⁻² to 10⁻⁶ S/cm, and a second polymeric film comprising a phosphorescent emitter comprising tris(2-(4-tolyl)phenylpyridine) iridium (III). 